JPS6135983B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to certain phthalimides substituted with alkenylamino groups and a method for producing the same. Thermosetting resins obtained by polyaddition reaction of N·N'-bis-imides of unsaturated dicarboxylic acids with primary diamines and curing of these resins or pre-adducts by thermal polymerization are disclosed in French Patent No. 1555564. It is stated in the specification. However, these resins require heating to bring the starting mixture of bis-imide and diamine to a suitably low viscosity, resulting in very short processing times and are therefore unsuitable for the manufacture of complex castings. Not yet. A molding containing the reaction product of an unsaturated dicarboxylic acid having two carbon-carbon double bonds with a N·N'-bis-imide, a polyamine and a monomer having a carbon-carbon double bond which can be polymerized by heating. Thermosetting composition for manufacturing products received German published patent no.
It is described in the specification of No. 2131735. The last-mentioned monomers in these compositions are in particular allyl derivatives such as allyl esters or allyl ethers or aromatic or heterocyclic compounds containing allyl substituents, in particular allyl O-phthalate, allyl cyanurate or triallyl trichloride. It can also be a melitate. The allyl compound is apparently added to reduce the viscosity of the starting mixture (bisimide+polyamine). However, due to the relatively short processing times, the resulting mixtures are very unsuitable for the production of complex castings, for filling cavities or interstices and for embedding objects in so-called disposable moldings. be. If it is desired to increase the time during which the composition can be used in a melted and castable state, that is, the processing time or the so-called pot life, aromatic compounds having 2 to 4 benzene rings can be used as polymerization modifiers. It is necessary to add up to 10% by weight of the imide, polyamine and monomer to the composition, so that a total of at least four different components are required for these thermosetting compositions. It is therefore an object of the present invention to provide thermosetting compositions with improved processing properties, storage stability, and without the above-mentioned disadvantages, in a simpler process. Therefore, the present invention provides compounds of the following formula: [wherein R ₁ is a lower alkyl group, having 2 to 5 carbon atoms]
an alkenyl group, an aryl group having 6 to 10 carbon atoms in the aryl part, or the following formula: {In the formula, Y is the following formula: (In the formula, R ₂ is

[Formula] (in the formula, R ₃ represents a hydrogen atom), and R ₃ represents the above meaning. ) represents a group represented by }, and R ₂ and R ₃ have the above meanings. ]Regarding a new phthalimide represented by. The phthalimides of the formula may be in the form of a mixture of 3- and 4-isomers. Surprisingly, when using the phthalimides according to the present invention represented by the formula and the polyimide having at least two groups containing carbon-carbon double bonds, storage stability is achieved even without the addition of polymerization regulators. It is possible to produce thermosetting compositions with suitably long processing times without admitting that their viscosity or the mechanical and electrical properties of the products that can be produced therefrom are compromised, so that these compositions The objects can also be used in the production of complex castings. The phthalimides of the present invention represented by the formula:
The following formula: (In the formula, Q ₁ and Q ₂ represent a hydroxyl group or -O- formed by Q ₁ and Q ₂ together,
And R ₂ and R ₃ have the meanings defined in the above formula. ) is a compound represented by the following formula: H ₂ N−R ₁ ′ ( ) [wherein R ₁ ′ is a lower alkyl group, having 2 to 5 carbon atoms]
an alkenyl group, an aryl group having 6 to 10 carbon atoms in the aryl part, or the following formula: represents a group represented by ] by reacting with a compound represented by the following formula: [In the formula, one of Q ₃ and Q ₄ represents a hydroxyl group, and the other represents -
NH-R ₁ ″ {wherein R ₁ ″ is a lower alkyl group, an alkenyl group having 2 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms in the aryl part, or the following formula: (In the formula, Y′ is the following formula: (In the formula, R ₂ and R ₃ have the above meanings.) ) represents a group represented by } represents. ] is obtained by cyclizing the compound represented by this formula. In the formula, R ₁ is a C 2 -C 5 alkenyl group, especially a C 2 -C 5 alkenyl group.

The phthalimide represented by [Formula] (in the formula, R ₃ represents the above meaning) can be expressed by the following formula: (In the formula, R ₂ and R ₃ represent the above meanings.) A compound represented by the following formula: Hal-alkenyl () (In the formula, Hal preferably represents a chlorine atom or a bromine atom, and the alkenyl group is a carbon It can also be produced by reacting it with an alkenyl halide (having 2 to 5 atoms) in the presence of an inorganic or organic base. The defined radicals R ₁ , R ₁ ′ or R ₁ ″ are unsubstituted or contain halogen atoms, such as chlorine, fluorine or bromine, or have 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms. May be substituted with an alkyl group or an alkoxy group.Alkyl group and alkenyl group R ₁ , R ₁ ' or
R ₁ '' and also the alkylene part of the substituent can be straight-chain or branched. Possible alkyl groups R ₁ , R ₁ ' or R ₁ '' include lower alkyl groups, especially from 1 to 4, especially unbranched. It is a substituted alkyl group. Examples include the following groups: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, alkenyl group R ₁ , R ₁ ′ or R ₁ ″ is unsubstituted. Preference is given to, for example, especially the methallyl group and especially the allyl group. Possible aryl groups R ₁ , R ₁ ′ or R ₁ ″ include, for example, in some cases chlorine, fluorine or bromine atoms. Mention may be made of phenyl groups and unsubstituted naphthyl groups substituted with halogen atoms or C1-C4 alkyl groups or alkoxy groups, in particular with 1 or 2 carbon atoms. Unsubstituted phenyl groups are preferred. The following formula: As a group represented by, in the same formula, Y is the following formula: (In the formula, R ₂ is

[Formula] (in the formula, R ₃ represents a hydrogen atom), and R ₃ represents the above meaning. ). Base:

[Formula] (wherein R ₂ and R ₃ represent the above meanings) is the 3-
It is preferable that the However, the phthalimides according to the invention and also the corresponding starting materials are
It is also possible to use mixtures of 3- and 4-alkenylamine substituted compounds. In particular, R ₁ is an unsubstituted alkyl group having 1 to 4 carbon atoms, an allyl group, a phenyl group or the following formula: represents a group represented by, and X is -CH ₂ - or -
Preferred are phthalimides represented by the formula O-, _R2 represents _-CH2 -CH= _CH2 , and _R3 represents a hydrogen atom. The starting compounds of formula and are new and can be prepared as follows. Compound represented by the following formula: The aminophthalic acid derivative represented by the following formula: By reacting with a compound represented by the following formula': and optionally converting the resulting phthalic acid derivative of formula ' into other derivatives of formula, for example by chemical cyclization or cyclization by the action of heat. It can be converted into the corresponding anhydride or into the corresponding monosalt or half-ester by reaction with suitable bases or alcohols in a manner known per se. In the above formulas and ', Q ₅ and Q ₆ each independently represent a hydroxyl group or a group -O ^- M ⁺ , and Hal
represents a halogen atom, in particular a chlorine or bromine atom, R ₂ and R ₃ have the meanings defined in the above formula and, and M ⁺ represents an alkali metal cation, a C 3 -C 24 trialkylammonium cation. ion or quaternary ammonium cation. When Q ₁ , Q ₂ , Q ₅ or Q ₆ represents −O ⁻ M ⁺ , M ⁺ is, for example, a lithium, sodium, potassium, trimethylammonium, triethylammonium, methyl-diethylammonium or tri-n-octylammonium anion. Represents an ion. M ⁺ representing the quaternary ammonium cation
represents, for example, penzyltrimethylammonium and tetramethylammonium cations.
Preferably M ⁺ represents a sodium cation. Compound represented by the formula By the reaction of a phthalic acid derivative represented by the formula ' with ammonia. The starting materials of the formula and are known or can be prepared by methods known per se. The reaction of a compound of the formula with a compound of the formula can be carried out in an inert organic solvent at a temperature of about 20 to 120°C, especially about 40 to 80°C, or in the melt. The compound of the formula is suitably reacted with a halide of the formula in an organic medium. Suitable inert organic solvents include, for example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic and cyclic ethers such as diethyl ether, tetrahydrofuran, tetrahydropyran and dioxane; dimethyl sulfoxide and diethyl sulfoxide. Dialkyl sulfoxides; N.
Mention may be made of N.N'.N'-tetramethylurea and tetrahydrothiophene dioxide (Sulpholane). Preferably, the solvent is toluene. The starting materials of the formula used are preferably the corresponding anhydrides. Inorganic or organic bases that can be used in the reaction of the compound represented by the formula with the halide of the formula include, for example, trimethylamine, triethylamine, pyridine, magnesium carbonate, calcium carbonate, potassium carbonate, sodium carbonate, lithium hydroxide, potassium hydroxide. and tertiary amines, pyridine, alkaline earth metal carbonates, hydroxides or carbons in the alkyl moiety, such as sodium hydroxide, magnesium methylate, potassium ethylate and sodium ethylate, potassium tert-butyrate and sodium tert-butyrate. Mention may be made of alcoholates having 1 to 4 atoms or alkali metal carbonates, hydroxides or alcoholates having 1 to 4 carbon atoms in the alkyl moiety. The cyclization of the compounds of the formula to the phthalimides of the formula can be carried out chemically or by the action of heat. The chemical cyclization is suitably carried out at temperatures of about 40 to 120°C in the presence of conventional dehydrating agents. Dehydrating agents that can be used include, in particular, those containing 2 to 2 carbon atoms, unsubstituted or substituted with halogen atoms or alkyl groups, such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride, trimethylacetic anhydride or triethyl acetic anhydride. 5 aliphatic monocarboxylic acid anhydrides are mentioned. Acetic anhydride is the preferred dehydrating agent. However, cyclization by the action of heat is generally preferred. For this purpose, the compound of the formula is advantageously heated to a temperature of about 100 to 180°C, preferably to a temperature of about 130 to 160°C. After completion of the reaction, the phthalimides of the invention of the formula can be isolated and, if necessary, purified by conventional methods, for example by distillation or by recrystallization from a suitable organic solvent, such as a mixture of hydrocarbons. The present invention also provides (a) a phthalimide represented by at least one formula; (b) per molecule the following formula: (wherein A represents a divalent group containing a carbon-carbon double bond) and optionally (c) polymerization initiation. and at least one phthalimide of the formula and at least one polyimide defined by each other, optionally in the presence of a polymerization initiator. The present invention relates to a method for producing crosslinked polymers containing imide groups. Many of the polyimides which can be used according to the invention are described in the following documents, for example British Patent No. 1066390, US Patent No. 3528950, French Patent No. 1555564 and German Published Patent Application No. See Publications No. 2230874 and No. 2350471. As polyimides, the following formula X: [In the formula, Z represents a divalent bond bridge member having 2 to 30 carbon atoms, and A represents -CH=CH-,

【formula】

【formula】 【formula】

【formula】

【formula】

【formula】

[formula] and especially

Bis-imides represented by the formula: (wherein A ₁ has the same meaning as A except for the last mentioned meaning) are preferred. In the above formula, A is the following formula: -CH=CH-,

【formula】

[Formula] and especially

[expression] or

Preference is given to compounds of the formula ##STR2## and Z is 4,4'-diphenylmethane or 4,4'-diphenyl ether. Possible bond bridge members Z include, in particular, carbon atoms of 2
to 12, especially 2 to 6 alkylene groups, unsubstituted or substituted phenylene or halogen atoms, such as chlorine, fluorine or bromine, or C1 to C4, especially 1 or 2 alkyl or alkoxy groups; Naphthylene group, cyclohexylene group and the following formula:

【formula】

【formula】

[expression] or

Examples include a group represented by the following formula: (wherein, X represents the meaning defined in the formula). However, oligoimides of the type described in DE 2230874 or of the following formula XI: Bis- and tris-imides of the formula can also be used in the compositions of the invention. In the above _formula
represents an oxygen atom or a sulfur atom, m represents 1 or 0, n represents 2 or 3, and
A ₂ is the following formula: −CH=CH−,

【formula】

[expression] or

[Formula] Represents a group represented by the following. Suitable polyimides include, for example, the following compounds: N.N'-ethylene-bis-maleimide, N.N'-hexamethylene-bis-nadoimide, N.N'-m- or -p-phenylene- Bis-maleimide, N・N'-p-tolylene-
Bis-maleimide, N・N′-p-cyclohexylene-bis-1,2,3,6-tetrahydrophdalimide, N・N′-m- or -p-xylylene-bis-citraconimide, N・N '-hexamethylene-bis-3,6-endoxo-1.
2,3,6-tetra-hydrophthalimide, N.
N', 4, 4'-dicyclohexylmethane-bis-maleimide, N, N', 4, 4'-diphenylmethane-
Bis-nadoimide, N・N′・4・4′-diphenylmethane-bis-maleimide, N・N′・4・4′-diphenyl ether-bis-maleimide, N・
N', 4, 4'-diphenylsulfone-bis-maleimide, N, N', α, β', 4, 4'-dimethylene-
Cyclohexane-bis-maleimide, N・N′・
4,4'-diphenylcyclohexane-bis-maleimide, N,N',4,4',2,2-diphenylpropane-bis-maleimide, N,N',γ,γ'-
1,3-dipropylene-5,5-dimethyl-hydantoin-bis-maleimide, N・N′・4・4′-
diphenylmethane-bis-dimethylmaleimide,
N・N′-hexamethylene-bis-dimethylmaleimide, N・N′・4・4′-diphenylmethane-
Bis-3-maleimidylphthalimide, N.
N′・4・4′-(diphenyl ether)-bis-3-
Nadoimidyl phthalimide, N.N'.4,4'-diphenylsulfone-bis-4-maleimidylphthalimide, 4,4'-diamino-triphenyl phosphate or 4,4'-diamino-triphenyl phthalimide. N.N'-bis-maleimide of the ophthalate and N.N'.N''-tris-maleimide of the tris-(4-aminophenyl) phosphate. and the following formula XII: (In the formula, A represents the meaning defined above.) It can be obtained by a method known per se by reacting with an anhydride represented by the following formula. Mixtures of two or more polyimides as defined above and/or mixtures of different phthalimides of the formula can also be used in the present invention. The molar ratio of phthalimide of the formula to polyimide as defined above can vary within a wide range. It is suitable to use compositions containing up to 50 mol % of phthalimide, preferably 5 to 30 mol %. Depending on the intended use, cationic, anionic or free-radical polymerization initiators, which are known per se, can also be added to the compositions according to the invention. Generally, these initiators are approximately
It is used in an amount of 0.01 to 5% by weight, preferably 0.01 to 1.5% by weight. For example, hydrogen peroxide, potassium peroxydisulfate, tert-butyl hydroperoxide, di-tert-butyl peroxide,
Free radicals of inorganic or organic peroxides or azo compounds such as peracetic acid, benzoyl peroxide, diacyl peroxide, cumene hydroperoxide, tert-butylpene benzoate, tertiary alkyl peroxy carbonate and α·α′-azoisobutyronitrile. Polymerization initiators are preferred. However, it is generally possible to omit the addition of a polymerization initiator. The phthalimides of the formula and the polyimides defined above are preferably reacted with each other in the melt or partially in the melt and partially in the solid phase. However, the reaction can also be carried out in solution. However, in many cases the addition of organic solvents is not necessary since the starting mixture itself already has a suitably low viscosity at temperatures above about 160°C.
The reaction in the melt is suitably carried out at a temperature of about 150 to 250°C, preferably 160 to 200°C. Suitable organic solvents that can be used for the reaction in solution include, for example, dioxane, tetrahydrofuran, tetramethylurea, dimethylformamide, dimethylacetamide and N-methylpyrrolidone. The processing of the composition according to the invention to give a crosslinked imide group-containing polymer can also be carried out in two steps. After mixing the starting materials and optionally following milling, the powder or liquid is first heated to about 150 to 220° C. for a limited period of time. During this time, a thermoplastic soluble prepolymer is formed as a function.
If desired, the prepolymer is ground again to a powder before further processing. However, the prepolymerization can also be carried out by heating a solution or suspension of the starting materials in the organic solvents mentioned above. The prepolymer is then heated to a final temperature of about 170 to 250°C.
It is cured by heating to a temperature of . The production of crosslinked polymers containing imide groups is
Generally, it is carried out to simultaneously form a molded article, a sheet-like molded article, a laminate, an adhesive layer, a foam, etc. Additives commonly used in the hardened plastics industry such as fillers, plasticizers, pigments, dyes, mold release agents and flame retardants can be added to the curable composition. Fillers that can be used include, for example, glass fibers, mica, graphite, quartz powder, kaolin, colloidal silica or metal powder. Materials that can be used as mold release agents include, for example, silicone oil, various wanoxes, zinc stearate or calcium stearate, and the like. The shaping of the products that can be produced with the compositions of the invention can be carried out in a very simple manner by the casting method using customary casting molds. However, the modeling is done at about 170 to 250 degrees Celsius.
It can also be carried out by a hot pressure method using a molding machine under a pressure of 100 to 450 kp/cm ² . The polymers which can be prepared with the compositions of the invention can be used in particular in the fields of casting manufacturing, surface protection, electrical engineering, lamination, adhesives and foam manufacturing, and in architecture. Example 1 24.3 g (0.1 mol) of 3-N.N-diallylaminophthalic anhydride was dissolved in 200 ml of toluene, 8.6 g (0.15 mol) of allylamine was added to the solution, and the mixture was stirred at 75-80 DEG C. for 2 hours. Then, toluene is distilled off and the residue is heated to 150 to 160℃.
The mixture was stirred for 1 hour. The cooled and solidified molten liquid is converted into gasoline with a special boiling point (mixture of hydrocarbons: boiling point
(110 to 130°C) was recrystallized from 120ml. 3-
Yield of N.N-diallylaminophthalic allylimide: 17.6 g = 81.5% of theory; melting point: 74°C Elemental analysis values (as C ₁₇ H ₁₈ N ₂ O ₂ ): C (%) H (%) N ( %) Calculated value 72.3 6.4 9.9 Actual value 72.3 6.5 9.9 3-N·N-diallylaminophthalic anhydride used in the above example was produced as follows:
225 g (1.0 mol) of disodium 3-aminophthalate and 138 g (1.0 mol) of potassium carbonate were added to 400 g of water.
ml. Allylpromide 317.2g (2.6
mol) was added to this solution at about 25°C and the reaction mixture was stirred at 30-35°C for 4 hours. Addition of 200 ml of 35% hydrochloric acid precipitated diallylamine phthalic acid. The product was filtered off at 10°C, washed with 100 ml of water and dried. Yield: 222g = theoretical amount of 85
%. 261g of this 3-diallylaminophthalic acid (1
mol) was heated to 150-155°C. A melt is formed which is heated at approximately 150°C for 2
Stir for an hour and then cool to 50°C. Then 750 ml of toluene and 750 ml of n-hexane were added and the crude product was recrystallized from this mixture. 3-N・N-
237 g of diallylaminophthalic anhydride (theoretical amount)
95%). Melting point 94-95℃. Example 2 By using an equivalent amount of n-propylamine in place of 8.6 g of allylamine in Example 1, and keeping the other points the same, 3-N·N-diallylaminophthalic acid n-propylimide was obtained. Melting point 65℃. Elemental analysis values (as C ₁₇ H ₂₀ N ₂ O ₂ ): C (%) H (%) N (%) Calculated value 71.8 7.1 9.9 Actual value 71.6 7.3 9.9 Example 3 In Example 1, allylamine was replaced with an equivalent amount of aniline. Perform the replacement and other steps in the same way, and perform 3.
-N.N-diallylaminophthalic acid phenylimide was obtained. Melting point: 93℃. Elemental analysis value (as C ₂₀ H ₁₈ N ₂ O ₂ ): C (%) H (%) N (%) Calculated value 75.4 5.7 8.8 Actual value 75.0 5.8 8.8 Example 4 In Example 1, 3-N・N - Diallylaminophthalic anhydride was replaced with an equivalent amount of 4-N.N-diallylaminophthalic anhydride, and the other conditions were the same to obtain 4-N.N-diallylaminophthalic allylimide. This product was still liquid at 20°C and was purified by distillation. Boiling point 150 to 170℃/0.003mmHg. Elemental analysis value (as C ₁₇ H ₁₈ N ₂ O ₂ ): C (%) H (%) N (%) Calculated value 72.3 6.4 9.9 Actual value 72.5 6.6 9.6 Example 5 In Example 1, 3-N・N - Replacing diallylaminophthalic anhydride with a 1:1 mixture of 3- and 4-N·N-diallylaminophthalic anhydride produces an isomer of 3- and 4-N·N-diallylaminophthalic allylimide. A 1:1 mixture was obtained. The product mixture was purified by distillation in a bulb tube oven. boiling point
150 to 170℃/0.002mmHg. Elemental analysis value (as C ₁₇ H ₁₈ N ₂ O ₂ ): C (%) H (%) N (%) Calculated value 72.3 6.4 9.9 Actual value 72.2 6.5 10.0 Example 6 9.9 g of 4,4'-diaminodiphenylmethane is added to a solution of 24.3 g (0.1 mol) of 3-N.N-diallylaminophthalic anhydride in 250 ml of toluene.
(0.05 mol) and heat the mixture at 80 to 85℃ for 2 hours.
Allowed time to react. Then all of the toluene was distilled off, the residue was dissolved in 100 ml of acetic anhydride, and the resulting solution was stirred at 120-125° C. for 30 minutes. After cooling, the precipitated product was filtered off and dried under reduced pressure.
26 g (80% of the theoretical amount) of bis-(4.4'-diphenylmethane)-3-N.N-diallylaminophthalimide represented by the above formula was obtained. Melting point 178 or more
179℃. Elemental analysis values (as C ₄₁ H ₃₆ N ₄ O ₄ ): C (%) H (%) N (%) Calculated value 75.9 5.6 8.6 Actual value 76.0 5.9 8.5 Example 7 4・4′-bis-maleimidyl-diphenylmethane (BMDM) 19.33 g (0.054 mol) and 1.69 g (0.006 mol) of 3-N·N-diallyl-aminophthalic allylimide prepared in Example 1 were thoroughly mixed together and the mixture was heated to 165° C. with occasional stirring. Heated. A melt is formed, which is divided into 4mm and 2mm
It was poured into an aluminum mold preheated to 180°C to produce thick sheets. In a circulating air oven at 180℃
Curing was carried out for 16 hours. The physical, summarized in the table below,
A transparent, bubble-free casting with mechanical and electrical properties was obtained. By adding the allyl derivative to bisimide in the above amount, the pot life could be extended to about 60%. Examples 8 to 14 Further castings were produced using the procedure described in Example 7. The molar ratios of the mixed components used, the curing conditions and the properties of the cured castings are summarized in the table. Furthermore, the cast product obtained in Example 8 showed no decrease in bending strength after aging at 240°C in air for 300 hours.

[Table] Example 15 12.89 g (0.036 mol) of 4,4'-bis-maleimidyl-diphenyl-methane (BMDM) and Example 2
The 3-N.N-diallyl-aminophthalic acid n-propylimide prepared above was thoroughly mixed together and the mixture was heated to 178-180 DEG C. with occasional stirring. After 3 minutes a low viscosity melt was formed which was kept at this temperature for 45 minutes. The gelled mixture formed at the end of this time was allowed to cool and ground to a fine powder. For processing by the compression molding method, the powder was placed in a compression mold for circular sheets preheated to 215° C. and compression molded at this temperature under a pressure of 350 kp/cm ² for 60 minutes. A transparent hard sheet was obtained. The electrical properties of the compression molded sheets are listed in the table. Examples 16 to 18 Further compression molded articles were produced using the procedure described in Example 15. The molar ratios of the mixed components used, the processing conditions and the electrical properties of the resulting compression molded articles are summarized in the following table.

[Table] Example 19 9.08 g (0.014 mol) of 4,4'-bis-(3-maleimidylphthalimide)-diphenylmethane and 3
-N・N-diallylaminophthalic acid allylimide
1.69 g (0.006 mol) were thoroughly mixed together and the mixture was heated to 200° C. with occasional stirring. The mixture, which was initially easily stirred, gradually became more viscous during this time. After heating at 200° C. for 50 minutes, the mixture was cooled and the solidified prepolymer was ground into a fine powder. For processing by the compression molding method, the powder was placed in a compression mold for circular sheets preheated to 220 °C and 450 kp/cm ²
Compression molding was carried out at this temperature under a pressure of 60 minutes. A transparent stiff sheet is obtained, which has good electrical properties when heat treated at 200°C for 16 hours. The 4,4'-bis-(3-maleimidyl-phthalimido)-diphenylmethane used in the above examples can be prepared as follows: 3-maleimidylphthalic anhydride (DE 2459673) 3-aminophthalic acid is reacted with maleic anhydride by the method disclosed in the publication, and the produced 3-
(produced by cyclizing maleimidylphthalic acid with anhydrous sodium acetate and acetic anhydride)
91.89 g (0.378 mol) was added to anhydrous N-N-dimethylacetamide in a sulfonation flask under nitrogen flow.
The solution was cooled to 0-5°C. Then, a solution of 35.68 g (0.18 mol) of 4,4'-diaminodiphenylmethane dissolved in 200 ml of DMA was added dropwise with stirring. After the addition was completed, the reaction mixture was further stirred at 20 to 25°C for 2 hours. Then 132 ml (1.44 mol) of acetic anhydride were added and the solution was heated to 80° C. for 2 hours with stirring. After cooling to about 20-25°C, the reaction product was precipitated with water.
The precipitate formed was filtered off, washed several times with water and dried in a vacuum oven at 80° C. for 20 hours. The reaction product was then boiled in approximately 10 times the weight of ethanol for 20 minutes, and the mixture was then filtered hot. After drying the product at 80℃ under high vacuum, 4,4'-bis-
107 g of (3-maleimidyl-phthalimido)-diphenylmethane were obtained in the form of a pale yellow powder with a melting point of 190 DEG to 210 DEG C. Example 20 Following the procedure described in Example 19, 5.19 g (0.008 mol) of 4,4'-bis-(3-maleimidyl-phthalimido)-diphenylmethane and 3-N.N-
Diallylaminophthalic acid allylimide 0.56g
(0.002 mol) was reacted at 200°C for 20 minutes. The resulting prepolymer was treated as described in the previous example.
After processing by compression molding method at 200-220°C, a transparent and stiff sheet with good electrical properties was obtained. Example 21 4.4'-bis-tetrahydrophthalimidyl diphenyl ether 1.84 g (0.004 mol), 3-N.
N-diallylaminophthalic acid allylimide 0.28g
(0.001 mol) and 4,4'-bis-maleimidyl-
0.18 g (0.0005 mol) of diphenylmethane was thoroughly mixed together and the mixture was heated to 215° C. for 1 hour.
After cooling, the molten mass was finely powdered and compression molded in a plate press at 230° C. for 10 minutes under contact pressure and 1 hour under 50 kp/cm ² to obtain a sheet. The 4,4'-bis-tetrahydrophthalimidyl-diphenyl tether used in the above examples was prepared as follows: 29.82 g (0.2 mol) of tetrahydrophthalic anhydride.
Dissolve in 120ml of anhydrous DMA, and make the solution between 0 and 5.
Cooled to ℃. Then, in 100ml of DMA, 4・4'-
A solution containing 20.02 g (0.1 mol) of diamino-diphenyl ether was added dropwise with stirring. 20
After stirring for 1 hour at 25 DEG C., 70 ml of toluene was added and the reaction solution was heated under reflux until no further water could be separated using a water separator. Then, toluene was distilled off, the reaction solution was poured into water, and the formed precipitate was washed several times with water. 44 g of 4,4'-bis-tetrahydrophthalimidyl-diphenyl ether in the form of a yellowish powder after drying in a vacuum dryer at 120°C.
(96% of theoretical amount) was obtained.

Claims (1)

[Claims] Primary formula: [In the formula, R ₁ is a lower alkyl group, having 2 to 5 carbon atoms
an alkenyl group, an aryl group having 6 to 10 carbon atoms in the aryl moiety, or the following formula: {In the formula, Y is the following formula: (In the formula, R ₂ represents a group represented by [Formula] (In the formula, R ₃ represents a hydrogen atom), and R ₃ represents the above _meaning .) and R ₃ have the above meanings. ] Phthalimides. 2 In the formula, R ₁ is an unsubstituted alkyl group having 1 to 4 carbon atoms, an allyl group, a phenyl group, or the following formula: represents a group represented by, and R ₂ is −CH ₂ −CH=
A compound according to claim 1, which represents CH ₂ and R ₃ represents a hydrogen atom. Cubic formula: [In the formula, Q ₁ and Q ₂ represent a hydroxyl group, or Q ₁ and Q ₂
represents a group formed by combining -O-, R ₂ represents [Formula] (in the formula, R ₃ represents the meaning given below), and R ₃ represents a hydrogen atom. ] A compound represented by the following formula: H ₂ N−R ₁ ′ ( ) [wherein R ₁ ′ is a lower alkyl group, having 2 to 5 carbon atoms.
an alkenyl group, an aryl group having 6 to 10 carbon atoms in the aryl part, or the following formula: represents a group represented by ] and react with a compound represented by the following formula: [In the formula, one of Q ₃ and Q ₄ represents a hydroxyl group, and the other represents -
NH-R ₁ ″ {wherein R ₁ ″ is a lower alkyl group, an alkenyl group having 2 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms in the aryl part, or the following formula: (In the formula, Y′ is the following formula: (In the formula, R ₂ and R ₃ have the above meanings.) ) represents a group represented by } represents. ], and the compound represented by this formula is cyclized: [In the formula, R ₁ is a lower alkyl group, having 2 to 5 carbon atoms
an alkenyl group, an aryl group having 6 to 10 carbon atoms in the aryl moiety, or the following formula: {In the formula, Y is the following formula: (In the formula, R ₂ represents a group represented by [Formula] (In the formula, R ₃ represents a hydrogen atom), and R ₃ represents the above _meaning .) and R ₃ have the above meanings. ] A method for producing phthalimides represented by 4. A method for producing a compound according to claim 3, wherein in the formula, _Q1 and _Q2 represent an -O- group formed together, and _R2 and _R3 have the above meanings.